Plating baths for depositing cobalt-lead nickel-lead alloys or combinations thereof and method of coating aluminum articles therewith

ABSTRACT

A method of plating cobalt-lead or nickel-lead alloys upon aluminum base articles. The plating baths comprise salts of the plating metals and have a pH of from 7-12. Both electroless and electroplating bath compositions are disclosed.

This is a division of application Ser. No. 589,992 filed June 24, 1975and now U.S. Pat. No. 3,970,237 which in turn was a continuation-in-partof application Ser. No. 304,457 filed Nov. 7, 1972, now abandoned.

BACKGROUND OF THE INVENTION

Prior to the instant invention, plating of aluminum with abond-promoting metal, such as nickel and/or cobalt, was accomplished bya variety of methods. Included in the prior methods were platingtechniques which employed acidic plating media, as for example, thetechnique set forth in U.S. Pat. No. 1,837,835. Also, a conventionalelectroless deposition from a hypophosphite solution is set forth inU.S. Pat. No. 2,532,283. The latter deposition provides bright coatingshaving aesthetic appeal, however, these coatings are inferior to thosecoatings provided by thermal decomposition or vacuum depositionprocesses when the coating is to be used in a bonding step. Thus, when acoated part prepared by conventional plating methods is employed in asubsequent bonding operation, the bond produced is often inadequate.

U.S. Pat. No. 3,482,305 discloses a brazing method wherein abond-promoting metal is used in conjunction with the brazing ofaluminum. The instant invention utilizes an improved bond-promotingplating where the plated aluminum article is to be bonded to anothermetal article, such as by brazing of aluminum, and optimizes the bondingprocess.

SUMMARY OF THE INVENTION

The instant invention relates to the brazing of one aluminum article toanother article which may be formed of aluminum or other metals and tothe method for plating of aluminum and aluminum alloys with abond-promoting metal.

Among the objects of the present invention is the provision of a methodof brazing one aluminum part to another part formed either of aluminumor another suitable metal or alloy. To accomplish the brazing operation,the aluminum part is plated with a bond-promoting metal, wherein analuminum braze-clad surface on the part or aluminum brazing foil to bepositioned between the parts is plated with the bond-promoting metalprior to brazing.

Another object of the present invention is the provision of a method ofplating aluminum or aluminum alloys with a bond-promoting metal ofnickel-lead, cobalt-lead or combinations thereof, in a form which isuniquely suited for subsequent bonding processes. The plating may beaccomplished by displacement, electroless or electrolytic means and isaccomplished under highly controlled conditions to achieve optimumresults.

A further object of the present invention is the provision of novelplating baths for either the electroless or electrolytic platingtechnique. The plating bath includes a nickel and/or cobalt salt and, inaddition lead salts in an amount of from about 50 ppm to about 10% ofthe total metal salts used to enhance the plating as a bond-promotingmetal.

Other objects and advantages of the invention will be apparent from thefollowing detailed description of the preferred embodiments thereof.

THE INVENTION

The instant invention relates to a method for brazing aluminum parts toother parts made of aluminum or other suitable metals, and also to themethod of plating of aluminum and aluminum alloys with a bond-promotingmetal of nickel, nickel-lead, cobalt, cobalt-lead and cobalt-nickel-leadcombinations for an aluminum alloy surface in a form which is uniquelysuited for subsequent bonding processes. The plating may be accomplishedby displacement, electroless or electrolytic means and is accomplishedunder highly controlled conditions to achieve optimum results. It isessential that the plating bath, comprised of given metal salts, bemaintained in an alkaline condition. Further, it has been found that theaddition of lead salts, in an amount of from about 50 ppm to about 10%of the total metal salts used, causes the plated coatings to beparticularly useful as a bond-promoting metal when used as such in asubsequent bonding step. The presence of the lead salt provides adeposition of the nickel-lead and/or cobalt-lead combinations to takethe form of finely divided sponge-like particles which are uniquelysuited to bonding processes by virtue of their high degree of action inpromoting the wetting of aluminum parts.

The composition of the plating bath will, of course, depend on the kindof deposition that is occurring, i.e., whether it is electroless orelectrolytic and the specific compositions are set forth in thespecification hereinbelow.

When plating is used as a step in the prior art brazing process ofjoining one aluminum part to another, a bond promoting alloy, forexample, nickel, cobalt or the like is plated on an aluminum braze-cladsurface, or on the surface of a foil made of brazing alloy, inpreparation for brazing. The brazing clad or brazing foil is an alloysuch as aluminum-silicon alloy. It is preferred that the bond-promotingalloy that is plated on the braze metal completely cover the brazingmetal. This requires at least 0.3 weight percent or 0.1 thicknesspercent of the total bond-promoting-alloy/brazing-alloy combination.Also, it is preferred that the amount of bond-promoting alloy not exceedabout 7 weight percent of the total alloy plate plus braze-metalcombination. If the amount does exceed about 7 weight percent, thebond-promoting metal, such as nickel, will react with the aluminum toform an excessive amount of aluminide film which is deleterious toproper bond formation. The thickness of the bond-promoting alloy platedon the aluminum brazing alloy is preferably about 0.1% to about 2.5% ofthe total thickness of the bond-promoting alloy-brazing alloycombination. The application of the plated coating, e.g., of nickel, issuch that upon heating, the nickel reacts with the aluminum and siliconof the brazing alloy, if such a combination is used, to form an eutecticthat will melt at 1050° F. In accordance with the prior art, filletformation results from favorable interfacial tension produced by theproper reaction of bond-promoting alloy and brazing metal which promotesthe wetting action of the resultant new brazing alloy. The process ofthe instant invention provides the bond-promoting metal plate in thenovel form of a finely divided sponge-like deposit which optimizesfillet formation in the brazing process by promoting the reaction of theplate with the brazing metal to produce a highly favorable wettingaction.

In the plating of the bond-promoting alloy onto the brazing alloy, suchas aluminum-silicon, cladding surface, or onto a brazing foil, a properplating bath must be provided. The plating as mentioned may occur eitheras displacement, electrolytic or electroless plating and the particularcombination disclosed by the instant invention of an alkaline mediacontaining an added lead salt is quite well applicable to all suchplating processes.

In the electrolytic plating of the bond-promoting alloy, such asnickel-lead or cobalt-lead, it is preferable that a metal salt, such asnickel or cobalt sulfate, be combined with a metal salt containing achloride ion such as nickel or cobalt chloride. It is also required thata lead ion be present in the form of a lead salt such as lead acetate.The bath is prepared which is basic in pH. The bath may be made basic byadding a base such as an alkali metal hydroxide or ammonium hydroxide.The total composition is buffered by adding a buffer, for example,sodium citrate or sodium gluconate. The temperature of the bath duringplating may vary from about 80° F. to about 160° F. and the pH rangesfrom 7 to about 12, i.e. on the basic side.

In the electroless plating of the bond-promoting alloy there is aplating solution similar to that of the electrolytic except that it isnot required that there be a chloride ion present provided by a metalsalt. The bond-promoting alloy in this process is plated by adisplacement, i.e., oxidation-reduction reaction. In the case of nickel,it is: 2Al° + 3Ni⁺ ⁺ → 2Al⁺ ⁺ ⁺ + 3Ni°. In other electroless processesthat could be used, nickel is plated by a reducing reaction, e.g.,NiSO₄ + NaH₂ PO₂ + H₂ O→ Ni° + NaH₂ PO₃ + H₂ SO₄. The bond-promotingalloys may be within the same class as those used in the electrolyticplating and illustrative ranges of components are set forth hereinbelowboth for the electrolytic and electroless plating bath.

In the tables hereinbelow, the illustrative baths show the percentage ofeach of the different components used for optimum plating of the alloyson an aluminum brazing-alloy surface.

                                      TABLE I                                     __________________________________________________________________________    Electroless Nickel-Lead Alloy Plating Bath                                    __________________________________________________________________________                         % Range                                                                              Preferred                   Preferred             Composition   Range  w/o**  Amount                                                                              w/o**                                                                             Substitute                                                                              Range   Amount                __________________________________________________________________________      Nickel Sulfate                                                                           30-200g/1                                                                             3.0-20.0                                                                             100.0g/l                                                                            10.0                                          Sodium Citrate                                                                           30-300g/l                                                                             3.0-30.0                                                                             200.0g/l                                                                            20.0                                                                              Sodium Gluconate                                                                        30-200g/l                                                                             150.0g/l                Lead Acetate                                                                             0.05-10.0g/l                                                                          0.005-1.0                                                                            1.0g/l                                                                               0.1                                                                              Lead Citrate or                                                                         0.05-5.0g/l                                                                           1.0g/l                                                      Bismuth Lactate                                                                         0.25-5.0g/l                                                                           1.0g/l                  Ammonium (NH.sub.3 =30%                                                                  25-150ml/l                                                                            2.5-15.0                                                                             75ml/l                                                                               7.5                                          Hydroxide                                                                     Temperature                                                                              180°-200°F.                                                                    180°F.                                     6*.                                                                             pH         7.0-12.0       10.5                                              __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________    Electroless Cobalt-Lead Alloy Plating Bath                                    __________________________________________________________________________                         % Range                                                                              Preferred                   preferred             Composition   Range  w/o**  Amount                                                                              w.o**                                                                             substitute                                                                              Range   Amount                __________________________________________________________________________      Cobalt Sulfate                                                                            30-200g/l                                                                            3.0-20.0                                                                             100.0g/l                                                                            10.0                                          Sodium Citrate                                                                            30-300g/l                                                                            3.0-30.0                                                                             200.0g/l                                                                            20.0                                                                              Sodium Gluconate                                                                        30-200g/l                                                                             150.0g/l                Lead Acetate                                                                              0.05-10.0g/l                                                                         0.005-1.0                                                                            1.0g/l                                                                               0.1                                                                              Lead Citrate or                                                                         0.05-5.0g/l                                                                           1.0g/l                                                      Bismuth Lactate                           Ammonium (NH.sub.3 =30%)                                                                  25-150ml/l                                                                           2.5-15.0                                                                             75ml/l                                                                               7.5                                          Hydroxide                                                                     Temperature 180°-200° F.                                                                  180° F.                                      pH          7.0-12.0      10.5                                              __________________________________________________________________________

                                      TABLE III                                   __________________________________________________________________________    Electroless Nickel-Cobalt-Lead Alloy Plating Bath                             __________________________________________________________________________                         % Range                                                                              Preferred                   Preferred             Composition   Range  w/o**  Amount                                                                              w/o**                                                                             Substitute                                                                              Range   Amount                __________________________________________________________________________      Nickel Sulfate                                                                           30-100g/l                                                                              3.0-10.0                                                                             50g/l                                                                              5.0                                           Cobalt Sulfate                                                                           100-30g/l                                                                              10.0-3.0                                                                             50g/l                                                                              5.0                                           Sodium Citrate                                                                           60-300g/l                                                                              6.0-30.0                                                                            200g/l                                                                               20.0                                                                             Sodium Gluconate                                                                        60-300g/l                                                                             150g/l                  Lead Acetate                                                                             0.05-10.0g/l                                                                           0.005-1.0                                                                           1.0g/l                                                                              0.1 Lead Citrate or                                                                         0.05-5.0g/l                                                                           1.0g/l                                                      Bismuth Lactate                           Ammonium (NH.sub.3 =30%)                                                                 25-150ml/l                                                                             2.5-15.0                                                                            75ml/l                                                                              7.5                                           Hydroxide                                                                     Temperature                                                                              180°-200° F.                                                                   180° F.                                                                      F                                           7*.                                                                             pH         7.0-12.0        0.5                                              __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________    Electrolytic Nickel-Lead Alloy Plating Bath                                   __________________________________________________________________________                         % Range                                                                              Preferred                   Preferred             Composition  Range   w/o**  Amount                                                                              w/o**                                                                             Substitute                                                                              Range   Amount                __________________________________________________________________________      Nickel Sulfate                                                                           30-200g/l                                                                             3.0-20.0                                                                              509/1                                                                              5.0                                           Nickel Chloride                                                                          100-10g/l                                                                             10.0-1.0                                                                              50g/l                                                                              5.0                                           Sodium Citrate                                                                           60-300g/l                                                                             6.0-30.0                                                                             100g/l                                                                               10.0                                                                             Sodium Gluconate                                                                        60-300g/l                                                                             150.0g/l                Lead Acetate                                                                             0.05-10.0g/l                                                                          0.005-1.0                                                                            1.0g/l                                                                              0.1 Lead Citrate or                                                                         0.05-5.0g/l                                                                           1.0g/l                                                      Bismuth Lactate                           Ammonium   5ml-150ml/l                                                                           0.5-15.0                                                                             75ml/l                                                                              7.5                                           Hydroxide                                                                     Temperature                                                                              80°-160° F.                                                                     80° F.                                    7*.                                                                             pH         7.0-12.0       10.5                10.5    10.5                  __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________    Electrolytic Cobalt-Lead Alloy Plating Bath                                   __________________________________________________________________________                         % Range                                                                              Preferred                   Preferred             Composition  Range   w/o*   Amount                                                                              w/o**                                                                             Substitute                                                                              Range   Amount                __________________________________________________________________________      Colbalt Sulfate                                                                          30-200g/l                                                                             3.0-20.0                                                                              50g/l                                                                              5.0                                           Cobalt Chloride                                                                          100-10g/l                                                                             10.0-1.0                                                                              50g/l                                                                              5.0                                           Sodium Citrate                                                                           60-300g/l                                                                             6.0-30.0                                                                             100g/l                                                                               10.0                                                                             Sodium Gluconate                                                                        60-300g/l                                                                             150.0g/l                Lead Acetate                                                                             0.05-10.0g/l                                                                          .005-1.0                                                                             1.0g/l                                                                              0.1 Lead Citrate or                                                                         0.05-5.0g/l                                                                           1.0g/l                                                      Bismuth Lactate                           Ammonium   5ml-175ml/l                                                                           0.5-7.5                                                                              75ml/l                                                                              7.5                                           Hydroxide                                                                     Temperature                                                                              80°-160° F.                                                                    80° F.                                     7*.                                                                             pH         7.0-12.0       10.5                10.5    10.5                  __________________________________________________________________________

                                      TABLE VI                                    __________________________________________________________________________    Electrolytic Nickel-Cobalt-Lead Alloy Plating Bath                            __________________________________________________________________________                         % Range                                                                              Preferred                   Preferred             Composition  Range   w/o**  Amount                                                                              w/o**                                                                             Substitute                                                                              Range   Amount                __________________________________________________________________________      Nickel Sulfate                                                                           30-300g/l                                                                             3.0-30.0                                                                              50g/l                                                                              5.0                                           Cobalt Chloride                                                                          100-10g/l                                                                             10.0-1.0                                                                              50g/l                                                                              5.0                                           Sodium Citrate                                                                           60-300g/l                                                                             6.0-30.0                                                                             100g/l                                                                               10.0                                                                             Sodium Gluconate                                                                        60-300g/l                                                                             150.0g/l                Lead Acetate                                                                             0.05-10.0g/l                                                                          .005-1.0                                                                             1.0g/l                                                                              0.1 Lead Citrate or                                                                         0.05-5.0g/l                                                                           1.0g/l                                                      Bismuth Lacate                            Ammonium   5-150ml/l                                                                             0.5-15.0                                                                             75ml/l                                                                              7.5                                           Hydroxide                                                                     Temperature                                                                              80°-160° F.                                                                     89° F.                                    7*.                                                                             pH         7.0-12.0       10.5                                              __________________________________________________________________________     *In each of the baths set forth in the tables the remaining percent to        total 100% is made up of water.                                               **Weight Percent.                                                        

It will be noted that the examples show plating solutions that have beenmade basic through the addition of ammonium hydroxide, however, otherbase solutions are equally operable. The addition of a base provides adeposit made up of small, spongy particles of bond promoting alloy whichare normally less than 100 microinches in diameter. The smaller theparticles, of course, the better will the surface be covered on thealuminum base alloy. The completely covered areas serve as nuclei forthe wetting action of the brazing alloy.

It has been found that the preferred thickness of the bond-promotingalloy, e.g. nickel-lead, on the aluminum-brazing alloy deposited throughthe plating process should be in excess of 3 microinches ofbond-promoting alloy as measured by an electrolytic dissolution method,employing for example a Kocour Electronic Thickness Tester, and theoptimum thickness is about 20 microinches. However, the amount ofnickel-lead alloy is dependent upon the brazing-alloy thickness and, aspreviously mentioned, should not exceed 7% by weight of the totalbrazing-alloy weight. Thus, when the braze-alloy is reduced to extremelythin coatings, which is normal in heat exchangers (especially in thinheat exchanger plates), the braze-alloy thickness can be as low as 1mil. In certain instances, it may be necessary, in order to keep belowthe 7% total nickel, to go below the preferred 20 microinches thicknessof nickel-lead. If excessive thickness is utilized, the nickel tends toreact with the aluminum to form an excessive amount of nickel aluminideand interfere with optimum fillet formation.

When the plating of the bond-promoting metal is used as a step inbrazing of one aluminum part to another, the parts are placed in contactwith each other in an inert atmosphere (either with or without pressure)at a temperature of from about 1050° F. to 1150° F. for a brief periodof time. The contact time is generally a couple of minutes to allowmelting and spreading of the brazing alloy and in turn cause a bond withthe bond-promoting metal.

Although the methods of the present invention are disclosed as primarilyemployed for the bonding of aluminum parts together, as in the thinaluminum plates of a heat exchanger, the methods are also useful for thebrazing or soldering of one part formed of aluminum or aluminum alloy toa second non-aluminum part formed of a metal or alloy, such as steel,stainless steel, nickel, nickel alloy, titanium or any aluminized metal.

More specifically, all aluminum alloys that can be brazed to each othercan be simultaneously brazed to the above-mentioned other metals, ifthese metals are coated with a deposit of nickel, nickel-lead, cobalt,cobalt-lead or combinations thereof. Nickel or cobalt or their alloyscan be brazed directly to the aluminum part without plating, if thealuminum filler alloy is coated with nickel, nickel-lead, cobalt,cobalt-lead or combinations thereof. Wettability of the surfaces ismarkedly improved if both members of the composite joints are coatedwith one of the plating materials. As with the brazing of aluminum partstogether, a key feature of this invention for brazing aluminum parts toparts of other metals is the reaction between the deposit of platingmaterial and the aluminum filler metal (aluminum braze clad) to form anew bonding alloy in situ at the joint, which in turn readily wets thecomposite components and promotes the flow of the brazing alloy into thejoints. Without the deposit of plating material, the mild steel andstainless steel surfaces were not wetted at all, but aluminized steelformed sound joints. The titanium alloy wetted only sporadically.

A series of experiments were conducted for the brazing of aluminum toother metals, with one part of the braze junction formed of an aluminumalloy sheet clad with a 10% silicon alloy. The aluminum component wascoated with an electroless nickel-lead or cobalt-lead alloy. Thefollowing metals, both with and without electroless nickel-lead orcobalt-lead alloy, were utilized as the second components in the brazingoperation: aluminized steel, mild steel, stainless steel and titanium.All coated specimens had the same thickness of electroless plating ofthe bond-promoting alloy and were brazed at 1120± 10° F. for fiveminutes in a nitrogen atmosphere of less than -60° F. dew point.

Considering each of the metal components, the aluminized steel brazed tothe aluminum alloy exhibited good wetting properties with generousfillets and complete bond along the interface where the specimen wasprecoated with the nickel-lead alloy. On the steel specimen not coatedwith the nickel alloy, a complete bond was formed in the interface butlower fluidity minimized the amount of fillet formation. Both types ofspecimens produced good joints with no evidence of cracking in the brazejunction.

For titanium without electroless nickel-lead, only occasional bondingoccurred where the two joint members were in close contact. There waslittle wetting and no fillet formation. However, on the coated titaniumspecimen, wetting was sufficient to form a complete bond with filletsalmost as large as in the aluminized steel specimen. An examination ofthe brazed joints showed that the nickel-lead deposit was lifted fromthe titanium and then reacted to form a continuous band of nickel-basedcompounds while suspended in the melt. There is a very little butdefinite reaction of the liquid brazing alloy with the titanium metal toform a thin layer of compound particles. There was no evidence ofcracking in the braze.

In the mild steel specimens, without the nickel-lead plating there wasno wetting of the mild steel even where there was intimate contactbetween the mild steel and aluminum alloy pieces. The nickel-lead coatedmild steel had good wetting action with generous fillet formation almostof the quality of the aluminized steel. The nickel deposits from boththe steel and aluminum pieces cause the formation of a continuous layerof nickel compounds, and there was no evidence of cracking in thespecimen.

Stainless steel behaved in the same manner as the mild steel withsubstantially no wettability without the nickel-lead coating and goodwetting with the coating. During the brazing cycle, the nickel depositsand the brazing alloy reacted with the stainless steel to form acontinuous compound layer, similar in appearance to that occurring onthe aluminized steel. However, some cracking did occur.

On the other hand, attempts to use copper for the other piece was notsuccessful. During the brazing cycle, the reaction between the liquidbrazing alloy, the copper and the aluminum sheet was so great as tocompletely melt the aluminum. These specimens were unsatisfactory.

Although the invention, set forth hereinabove, has been illustrated withreference to certain specific bond-promoting metal salts and certainlead salts, the plating may be accomplished with other substituents thanthose specifically set forth. Modifications in the plating methods willbe apparent to those skilled in the art of plating and the scope of theinvention is defined by the claims which are appended hereto.

I claim:
 1. In a process for plating on aluminum and aluminum alloysurfaces, metals selected from the group consisting of nickel, cobaltand combinations thereof employing an aqueous plating bath containingthe dissolved salts of the plating metals and buffering salts, thecombination wherein:the pH of said plating bath is maintained in therange of from pH 7 to about pH 12 by the addition of a base selectedfrom the group consisting of alkali metal hydroxides and ammoniumhydroxide, and from about 0.005% by weight to about 1.0% by weight of alead salt based on the total plating bath composition is added thereto,whereby the resultant plating on the aluminum and aluminum alloysurfaces is deposited in the form of small, finely divided sponge-likeparticles not exceeding 100 microinches in diameter.
 2. The combinationof claim 1 wherein the base employed is ammonium hydroxide.
 3. Thecombination of claim 1 wherein the base employed is ammonium hydroxideand the pH of the plating bath is maintained in the range of 10.0 to11.0.
 4. The combination of claim 3 wherein the lead salt is selectedfrom the group consisting of lead acetate and lead citrate.
 5. A platingbath for electrodepositing on aluminum and aluminum alloy surfacesmetals selected from the group consisting of nickel-lead, cobalt-leadand combinations thereof, consisting of an aqueous solution of:fromabout 3 to about 20 weight percent of a metal sulfate selected from thegroup consisting of nickel sulfate and cobalt sulfate, and from about 3to about 10 weight percent of a metal chloride selected from the groupconsisting of nickel chloride and cobalt chloride, and from about 6 toabout 30 weight percent of a buffering salt selected from the groupconsisting of sodium citrate and sodium glyconate, and from about 0.005to about 1.0 weight percent of a lead salt selected from the groupconsisting of lead acetate and lead citrate; the said plating bath beingadjusted to a pH value in the range of 7 to
 12. 6. A plating bath forelectroless deposition on aluminum and aluminum alloy surfaces metalsselected from the group consisting of nickel-lead, cobalt-lead andcombinations thereof, consisting of an aqueous solution of:from about 3to about 20 weight percent of at least one metal sulfate selected fromthe group consisting of nickel sulfate and cobalt sulfate, and fromabout 3 to about 30 weight percent of a buffering salt selected from thegroup consisting of sodium gluconate and sodium citrate, and from about0.005 to about 1.0 weight percent of a lead salt selected from the groupconsisting of lead acetate and lead citrate; the said plating bath beingneutralized to a pH value in the range of 8 to
 12. 7. A plating bath forthe deposition on aluminum and aluminum alloy surfaces of metalsselected from the group of nickel-lead, cobalt-lead and combinationsthereof, comprising an aqueous bath containing the dissolved salts ofthe plating metals and buffering salts, whereinthe pH of said bath ismaintained in the range of from pH 7 to about pH 12 by the addition of abase selected from the group consisting of alkali metal hydroxides andammonium hydroxide, and from about 0.005% by weight to about 1.0% byweight of a lead salt based on the total plating bath composition isadded thereto, whereby the resultant plating on the aluminum andaluminum alloy surfaces is deposited in the form of small, finelydivided sponge-like particles not exceeding 100 micro-inches indiameter.
 8. The plating bath as set forth in claim 7, wherein the baseemployed is ammonium hydroxide.
 9. The plating bath as set forth inclaim 7, wherein the base employed is ammonium hydroxide and the pH ofthe bath is maintained in the range of 10.0 to 11.0.
 10. The platingbath as set forth in claim 7, wherein the lead salt is selected from thegroup consisting of lead acetate and lead citrate.
 11. The plating bathas set forth in claim 7, wherein the metal salt is a metal sulfateselected from the group consisting of nickel sulfate and cobalt sulfate.12. The plating bath as set forth in claim 7, wherein the buffering saltis selected from the group consisting of sodium citrate and sodiumgluconate.
 13. The plating bath as set forth in claim 7, where the metalsalts are a metal sulfate selected from the group consisting of nickelsulfate and cobalt sulfate and a metal chloride selected from the groupconsisting of nickel chloride and cobalt chloride.